Adam Fahy

Reduced Uranium Phases Produced from Anaerobic Reaction with Nanoscale Zerovalent Iron

Nanoscale zerovalent iron (nZVI) has shown potential to be an effective remediation agent for uranium-contaminated subsurface environments, however, the nature of the reaction products and their formation kinetics have not been fully elucidated over a range of environmentally relevant conditions. In this study, the oxygen-free reaction of U(VI) with varying quantities of nZVI was examined at pH 7 in the presence of both calcium and carbonate using a combination of X-ray absorption spectroscopy, X-ray diffraction and transmission electron microscopy. It was observed that the structure of the reduced U solid phases was time dependent and largely influenced by the ratio of nZVI to U in the system. At the highest U:Fe molar ratio examined (1:4), nanoscale uraninite (UO2) was predominantly formed within 1 day of reaction. At lower U:Fe molar ratios (1:21), evidence was obtained for the formation of sorbed U(IV) and U(V) surface complexes which slowly transformed to UO2 nanoparticles that were stable for up to 1 year of anaerobic incubation. After 8 days of reaction at the lowest U:Fe molar ratio examined (1:110), sorbed U(IV) was still the major form of U associated with the solid phase. Regardless of the U:Fe molar ratio, the anaerobic corrosion of nZVI resulted in the slow formation of micron-sized fibrous chukanovite (Fe2(OH)2CO3) particles.

Unlocking new contrast in a scanning helium microscope

Delicate structures (such as biological samples, organic films for polymer electronics and adsorbate layers) suffer degradation under the energetic probes of traditional microscopies. Furthermore, the charged nature of these probes presents difficulties when imaging with electric or magnetic fields, or for insulating materials where the addition of a conductive coating is not desirable. Scanning helium microscopy is able to image such structures completely non-destructively by taking advantage of a neutral helium beam as a chemically, electrically and magnetically inert probe of the sample surface. Here we present scanning helium micrographs demonstrating image contrast arising from a range of mechanisms including, for the first time, chemical contrast observed from a series of metal–semiconductor interfaces. The ability of scanning helium microscopy to distinguish between materials without the risk of damage makes it ideal for investigating a wide range of systems.

Field emission from single-, double-, and multi-walled carbon nanotubes chemically attached to silicon

The chemical attachment and field emission (FE) properties of single-walled carbon nanotubes (SWCNTs), double-walled carbon nanotubes (DWCNTs), and multi-walled carbon nanotubes (MWCNTs) chemically attached to a silicon substrate have been investigated. A high density of CNTs was revealed by atomic force microscopy imaging with orientation varying with CNT type. Raman spectroscopy was used to confirm the CNT type and diameter on the surfaces. The field emission properties of the surfaces were studied and both current-voltage and Fowler-Nordheim plots were obtained. The SWCNTs exhibited superior FE characteristics with a turn-on voltage (Eto) of 1.28 V μm−1 and electric field enhancement factor (β) of 5587. The DWCNT surface showed an Eto of 1.91 V μm−1 and a β of 4748, whereas the MWCNT surface exhibited an Eto of 2.79 V μm−1 and a β of 3069. The emission stability of each CNT type was investigated and it was found that SWCNTs produced the most stable emission. The differences between the FE characteristi...

A highly contrasting scanning helium microscope.

We present a scanning helium microscope equipped to make use of the unique contrast mechanisms, surface sensitivity, and zero damage imaging the technique affords. The new design delivers an order of magnitude increase in the available helium signal, yielding a higher contrast and signal-to-noise ratio. These improvements allow the microscope to produce high quality, intuitive images of samples using topological contrast, while setting the stage for investigations into further contrast mechanisms.

Manipulating the orientation of an organic adsorbate on silicon: a NEXAFS study of acetophenone on Si(0 0 1)

We investigate the chemical and structural configuration of acetophenone on Si(0 0 1) using synchrotron radiation core-level spectroscopy techniques and density functional theory calculations. Samples were prepared by vapour phase dosing of clean Si(0 0 1) surfaces with acetophenone in ultrahigh vacuum. Near edge x-ray absorption fine structure spectroscopy and photoelectron spectroscopy measurements were made at room temperature as a function of coverage density and post-deposition anneal temperature. We show that the dominant room temperature adsorption structure lies flat on the substrate, while moderate thermal annealing induces the breaking of Si-C bonds between the phenyl ring and the surface resulting in the reorientation of the adsorbate into an upright configuration.

A desktop supersonic free-jet beam source for a scanning helium microscope (SHeM)

A simple design for an inexpensive, compact, desktop-sized helium free-jet beam source is described. The apparatus, which is Campargue-like in design and utilizes mostly off-the-shelf parts, is capable of producing a centreline intensity of 1.2???1019?atoms per second per steradian. The beam performance was investigated using a conventional ion gauge and a stagnation detector, with the latter being used to produce beam flux profiles. The profile of the macroskimmed beam has been experimentally demonstrated to be strongly Gaussian.

Improved field emission stability from single-walled carbon nanotubes chemically attached to silicon

Here, we demonstrate the simple fabrication of a single-walled carbon nanotube (SWCNT) field emission electrode which shows excellent field emission characteristics and remarkable field emission stability without requiring posttreatment. Chemically functionalized SWCNTs were chemically attached to a silicon substrate. The chemical attachment led to vertical alignment of SWCNTs on the surface. Field emission sweeps and Fowler-Nordheim plots showed that the Si-SWCNT electrodes field emit with a low turn-on electric field of 1.5 V μm−1 and high electric field enhancement factor of 3,965. The Si-SWCNT electrodes were shown to maintain a current density of >740 μA cm−2 for 15 h with negligible change in applied voltage. The results indicate that adhesion strength between the SWCNTs and substrate is a much greater factor in field emission stability than previously reported.

The short-term reduction of uranium by nanoscale zero-valent iron (nZVI): role of oxide shell, reduction mechanism and the formation of U(V)-carbonate phases

Nanoscale zero-valent iron (nZVI) is a potential remediation agent for uranium-contaminated groundwaters, however, a complete mechanistic understanding of the processes that lead to uranium immobilization has yet to be achieved. In this study, the short-term anoxic reaction of U(VI) with fresh, (anoxic) aged and corroded nZVI particles was investigated under aqueous conditions conducive to the formation of thermodynamically stable U(VI)–Ca–CO3 ternary aqueous complexes. The first stage of the reaction between U(VI) and nZVI was assigned to sorption processes with the formation of surface U(VI)-carbonate complexes. Aged nZVI removed U(VI) faster than either fresh or corroded nZVI and it is hypothesized that U reduction initially occurs through the transfer of one electron from Fe(II) in the nZVI surface oxide layer. Evidence for reduction to U(V) was obtained through X-ray photoelectron spectroscopy and by determination of U–O bond distances of ∼2.05 A and 2.27 A, using U LIII-edge X-ray absorption spectroscopy, which are similar to those observed for the U(V) site in the mixed U(V)/U(VI) carbonate mineral wyartite. Scanning transmission electron microscopy also demonstrated that U was present as a nanoparticulate phase after one day of reaction, rather than a surface complex. Further reduction to U(IV), as observed in previous studies, would appear to be rate-limiting and coincident with the transformation of this meta-stable U-carbonate phase to uraninite (UO2).

Development of an improved field ionization detector incorporating a secondary electron stage

Field ionization from sharp tips is attracting increased attention for use in detectors for neutral atomic/molecular species. However, the direct detection of the ionized species typically results in low sensitivities due to the small acceptance angle of the receiving ion-sensitive measurement device (usually a channel electron multiplier) and can result in sputtering damage due to the relatively high mass and energy of the incident ion species. Here we present a design for a field-ionization-based neutral atom detector incorporating a simple secondary electron generating stage. The use of such a stage decouples the field-ionized species from the detected electron signal, thus eliminating any sputtering damage to the channel electron multiplier. The detector armature discussed is shown to exhibit a linear response to neutral gas pressure and a sensitivity that is improved by more than two orders of magnitude over a previous field ionization detector design.

A simple counter-flow cooling system for a supersonic free-jet beam source assembly

A simple design for an inexpensive, cooled, free-jet beam source is described. The source assembly features an integrated cooling system as supplied by a counter-flow of chilled nitrogen, and is composed primarily of off-the-shelf tube fittings. The design facilitates rapid implementation and eases subsequent alignment with respect to any downstream beamline aperture. The source assembly outlined cools the full length of the stagnation volume, offering temperature control down to 100 K and long-term temperature stability better than ±1 K.